Buy article online - an online subscription or single-article purchase is required to access this article.
Two polymorphic forms of a mixed zinc/copper biquinoline dihydrogenphosphate are presented, showing almost identical monomeric units, viz. (2,2′-biquinoline-κ2N,N′)bis(dihydrogenphosphato-κO)copper(II)/zinc(II), formulated as [ZnxCu1−x(H2PO4)2(C18H12N2)], with x = 0.88 (1) and 0.90 (2). The cation is tetrahedrally coordinated to a chelating biquinoline system and two diprotonated phosphate anions. The structures differ mainly in their intermolecular hydrogen-bonding interactions, leading to different packing schemes. No significant evidence of stress due to the Zn/Cu solid solution formation was detected.
Supporting information
CCDC references: 652490; 652491
The original scope of the synthesis was to obtain a hybrid organic–inorganic
compound, that is, one with an inorganic structure as a host
(···-P—O—V-···) and a metal–biquinoline complex as a guest (Feng & Xu,
2001). In the process of adjusting the hydrothermal conditions the mixed
zinc/copper complex reported here was obtained serendipitously. For the
synthesis, a mixture of Cu(NO3)2·3H2O (0.5 mmol), V2O5 (0.25 mmol), 2,2-biquinoline (1.0 mmol), H3PO4 (5 ml, 0.0087 mmol) and Zn (0.5 mmol) was sealed in a Teflon-lined acid digestion bomb, heated at 393 K for 6 d under autogenous pressure and then cooled slowly at 20 K h-1 to room
temperature. The resulting solid product consisted of a mixture of orange
crystals pertaining to both polymorphs, which could be clearly distinguished
because of their different crystal shapes. A combination of UV–vis
spectroscopy and EDAX analysis confirmed the existence of mixed cationic sites
with similar occupancies in both polymorphs [polymorph (I) Zn0.88Cu0.12
and polymorph (II) Zn0.90Cu0.10].
H atoms in the organic ligand were placed at calculated positions (C—H = 0.93 Å) and allowed to ride. Those in the dihydrogenphosphate groups were found
in a difference Fourier synthesis and refined with restrained O—H distances
of 0.82 (2) Å. All H atoms were assigned a Uiso(H) values of
1.2Ueq(host). Owing to the impossibility of differentiating Zn from
Cu through refinement methods, the occupancies of the mixed cationic sites
were taken as the average result coming out of the compositional analysis
(UV–vis spectroscopy and EDAX), which gave x = 0.88 (5) for (I) and
x = 0.90 (4) for (II), values which were kept fixed during refinement.
For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 2000); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2000) and PLATON (Spek, 2003).
(I) (2,2'-biquinoline-
κ2N,
N')bis(dihydrogenphosphato-
κO)copper(II)/zinc(II) (0.88/0.12)
top
Crystal data top
[Zn0.88Cu0.12(H2PO4)2(C18H12N2)] | Z = 2 |
Mr = 515.42 | F(000) = 523.8 |
Triclinic, P1 | Dx = 1.761 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8089 (12) Å | Cell parameters from 4467 reflections |
b = 10.5225 (17) Å | θ = 3.7–25.1° |
c = 12.3618 (19) Å | µ = 1.46 mm−1 |
α = 91.787 (2)° | T = 298 K |
β = 91.722 (2)° | Blocks, orange |
γ = 106.632 (3)° | 0.26 × 0.12 × 0.08 mm |
V = 972.0 (3) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4216 independent reflections |
Radiation source: fine-focus sealed tube | 3529 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
phi and ω scans | θmax = 28.1°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −10→9 |
Tmin = 0.79, Tmax = 0.89 | k = −13→13 |
7214 measured reflections | l = −16→15 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0585P)2 + 0.642P] where P = (Fo2 + 2Fc2)/3 |
4216 reflections | (Δ/σ)max = 0.009 |
292 parameters | Δρmax = 0.68 e Å−3 |
4 restraints | Δρmin = −0.38 e Å−3 |
Crystal data top
[Zn0.88Cu0.12(H2PO4)2(C18H12N2)] | γ = 106.632 (3)° |
Mr = 515.42 | V = 972.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8089 (12) Å | Mo Kα radiation |
b = 10.5225 (17) Å | µ = 1.46 mm−1 |
c = 12.3618 (19) Å | T = 298 K |
α = 91.787 (2)° | 0.26 × 0.12 × 0.08 mm |
β = 91.722 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4216 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3529 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.89 | Rint = 0.025 |
7214 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 4 restraints |
wR(F2) = 0.136 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.68 e Å−3 |
4216 reflections | Δρmin = −0.38 e Å−3 |
292 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.46617 (5) | 0.77449 (3) | 0.27694 (3) | 0.03122 (10) | 0.88 |
Cu1 | 0.46617 (5) | 0.77449 (3) | 0.27694 (3) | 0.03122 (10) | 0.12 |
P1 | 0.14005 (11) | 0.52919 (8) | 0.35059 (7) | 0.02984 (19) | |
P2 | 0.60503 (11) | 0.55989 (8) | 0.16354 (7) | 0.0330 (2) | |
O1 | 0.2544 (4) | 0.6637 (3) | 0.3266 (3) | 0.0650 (9) | |
O2 | −0.0510 (3) | 0.5230 (2) | 0.36773 (18) | 0.0390 (6) | |
O3 | 0.1484 (3) | 0.4287 (2) | 0.2576 (2) | 0.0443 (7) | |
H3P | 0.240 (3) | 0.458 (4) | 0.224 (2) | 0.053* | |
O4 | 0.2181 (3) | 0.4792 (3) | 0.4517 (2) | 0.0571 (8) | |
H4P | 0.164 (4) | 0.481 (4) | 0.5083 (19) | 0.069* | |
O5 | 0.6316 (4) | 0.6855 (3) | 0.2305 (3) | 0.0671 (9) | |
O6 | 0.4151 (3) | 0.4854 (3) | 0.13092 (19) | 0.0426 (6) | |
O7 | 0.7153 (4) | 0.5987 (4) | 0.0621 (2) | 0.0735 (11) | |
H7P | 0.664 (5) | 0.569 (5) | 0.002 (2) | 0.088* | |
O8 | 0.6866 (4) | 0.4649 (2) | 0.2257 (2) | 0.0547 (8) | |
H8P | 0.768 (3) | 0.501 (4) | 0.271 (2) | 0.066* | |
N1 | 0.4098 (3) | 0.9084 (2) | 0.1772 (2) | 0.0290 (6) | |
N2 | 0.5996 (3) | 0.9419 (2) | 0.3623 (2) | 0.0279 (6) | |
C1 | 0.2997 (4) | 0.8804 (3) | 0.0857 (3) | 0.0303 (7) | |
C2 | 0.2188 (5) | 0.7476 (3) | 0.0512 (3) | 0.0389 (9) | |
H2 | 0.2386 | 0.6789 | 0.0906 | 0.047* | |
C3 | 0.1114 (5) | 0.7203 (4) | −0.0400 (3) | 0.0428 (9) | |
H3 | 0.0587 | 0.6325 | −0.0634 | 0.051* | |
C4 | 0.0789 (5) | 0.8228 (4) | −0.0993 (3) | 0.0432 (9) | |
H4 | 0.0047 | 0.8025 | −0.1615 | 0.052* | |
C5 | 0.1548 (5) | 0.9516 (4) | −0.0668 (3) | 0.0394 (8) | |
H5 | 0.1319 | 1.0187 | −0.1068 | 0.047* | |
C6 | 0.2676 (4) | 0.9844 (3) | 0.0267 (3) | 0.0332 (8) | |
C7 | 0.3508 (4) | 1.1158 (3) | 0.0647 (3) | 0.0358 (8) | |
H7 | 0.3310 | 1.1861 | 0.0275 | 0.043* | |
C8 | 0.4592 (4) | 1.1406 (3) | 0.1550 (3) | 0.0338 (8) | |
H8 | 0.5136 | 1.2274 | 0.1803 | 0.041* | |
C9 | 0.4887 (4) | 1.0328 (3) | 0.2101 (2) | 0.0268 (7) | |
C10 | 0.6037 (4) | 1.0530 (3) | 0.3113 (2) | 0.0289 (7) | |
C11 | 0.7073 (5) | 1.1776 (3) | 0.3504 (3) | 0.0342 (8) | |
H11 | 0.7112 | 1.2529 | 0.3119 | 0.041* | |
C12 | 0.8028 (4) | 1.1876 (3) | 0.4457 (3) | 0.0349 (8) | |
H12 | 0.8731 | 1.2703 | 0.4724 | 0.042* | |
C13 | 0.7961 (4) | 1.0742 (3) | 0.5041 (3) | 0.0299 (7) | |
C14 | 0.8882 (4) | 1.0785 (4) | 0.6058 (3) | 0.0387 (8) | |
H14 | 0.9565 | 1.1594 | 0.6370 | 0.046* | |
C15 | 0.8765 (5) | 0.9656 (4) | 0.6567 (3) | 0.0428 (9) | |
H15 | 0.9368 | 0.9693 | 0.7233 | 0.051* | |
C16 | 0.7747 (5) | 0.8414 (4) | 0.6113 (3) | 0.0431 (9) | |
H16 | 0.7689 | 0.7645 | 0.6479 | 0.052* | |
C17 | 0.6852 (5) | 0.8336 (3) | 0.5144 (3) | 0.0362 (8) | |
H17 | 0.6186 | 0.7515 | 0.4845 | 0.043* | |
C18 | 0.6931 (4) | 0.9498 (3) | 0.4592 (3) | 0.0306 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0376 (2) | 0.01878 (17) | 0.0348 (2) | 0.00407 (15) | 0.00184 (16) | 0.00067 (14) |
Cu1 | 0.0376 (2) | 0.01878 (17) | 0.0348 (2) | 0.00407 (15) | 0.00184 (16) | 0.00067 (14) |
P1 | 0.0331 (4) | 0.0246 (4) | 0.0290 (4) | 0.0032 (3) | 0.0069 (3) | 0.0008 (3) |
P2 | 0.0344 (4) | 0.0294 (4) | 0.0362 (4) | 0.0114 (3) | −0.0005 (4) | −0.0020 (3) |
O1 | 0.0725 (17) | 0.0282 (13) | 0.088 (2) | −0.0006 (13) | 0.0463 (16) | −0.0014 (13) |
O2 | 0.0366 (12) | 0.0513 (14) | 0.0304 (11) | 0.0141 (11) | 0.0031 (10) | 0.0068 (10) |
O3 | 0.0474 (14) | 0.0360 (13) | 0.0408 (13) | −0.0019 (11) | 0.0143 (11) | −0.0104 (11) |
O4 | 0.0470 (13) | 0.102 (2) | 0.0338 (13) | 0.0386 (14) | 0.0060 (11) | 0.0071 (14) |
O5 | 0.0533 (15) | 0.0484 (15) | 0.104 (2) | 0.0269 (12) | −0.0166 (16) | −0.0342 (15) |
O6 | 0.0345 (12) | 0.0568 (15) | 0.0338 (12) | 0.0093 (11) | 0.0032 (10) | −0.0062 (11) |
O7 | 0.0463 (16) | 0.110 (3) | 0.0424 (16) | −0.0131 (17) | −0.0022 (13) | 0.0121 (17) |
O8 | 0.0660 (17) | 0.0316 (13) | 0.0625 (17) | 0.0108 (12) | −0.0282 (14) | 0.0007 (12) |
N1 | 0.0333 (13) | 0.0232 (12) | 0.0289 (13) | 0.0055 (11) | 0.0017 (11) | 0.0011 (10) |
N2 | 0.0320 (13) | 0.0222 (12) | 0.0293 (13) | 0.0075 (10) | 0.0022 (11) | −0.0006 (10) |
C1 | 0.0289 (14) | 0.0327 (16) | 0.0288 (15) | 0.0084 (13) | 0.0026 (13) | 0.0001 (13) |
C2 | 0.0475 (19) | 0.0272 (16) | 0.0371 (18) | 0.0030 (15) | 0.0003 (16) | 0.0029 (14) |
C3 | 0.0406 (19) | 0.0380 (19) | 0.0425 (19) | 0.0010 (16) | −0.0028 (16) | −0.0075 (16) |
C4 | 0.0379 (18) | 0.055 (2) | 0.0361 (18) | 0.0139 (16) | −0.0074 (15) | −0.0029 (16) |
C5 | 0.0393 (17) | 0.0454 (19) | 0.0354 (18) | 0.0154 (15) | −0.0036 (15) | 0.0043 (15) |
C6 | 0.0327 (15) | 0.0356 (17) | 0.0319 (16) | 0.0103 (14) | 0.0060 (13) | 0.0019 (13) |
C7 | 0.0417 (17) | 0.0291 (15) | 0.0410 (18) | 0.0165 (14) | 0.0044 (15) | 0.0067 (14) |
C8 | 0.0434 (17) | 0.0229 (15) | 0.0352 (17) | 0.0093 (13) | 0.0037 (14) | 0.0027 (13) |
C9 | 0.0312 (14) | 0.0229 (14) | 0.0258 (14) | 0.0066 (12) | 0.0043 (12) | 0.0003 (11) |
C10 | 0.0326 (15) | 0.0254 (14) | 0.0292 (15) | 0.0083 (12) | 0.0081 (13) | 0.0006 (12) |
C11 | 0.0456 (18) | 0.0226 (15) | 0.0327 (16) | 0.0072 (14) | 0.0023 (14) | 0.0005 (12) |
C12 | 0.0380 (17) | 0.0244 (15) | 0.0394 (18) | 0.0041 (13) | 0.0063 (15) | −0.0038 (13) |
C13 | 0.0321 (15) | 0.0281 (15) | 0.0292 (15) | 0.0081 (13) | 0.0049 (13) | −0.0042 (12) |
C14 | 0.0349 (16) | 0.0407 (18) | 0.0404 (19) | 0.0122 (15) | −0.0011 (15) | −0.0087 (15) |
C15 | 0.0407 (17) | 0.055 (2) | 0.0377 (19) | 0.0230 (16) | −0.0042 (15) | −0.0005 (16) |
C16 | 0.0485 (19) | 0.0427 (19) | 0.044 (2) | 0.0217 (16) | 0.0058 (17) | 0.0111 (16) |
C17 | 0.0410 (17) | 0.0282 (16) | 0.0404 (18) | 0.0110 (14) | 0.0017 (15) | 0.0042 (14) |
C18 | 0.0278 (14) | 0.0305 (16) | 0.0341 (16) | 0.0094 (13) | 0.0057 (13) | 0.0004 (13) |
Geometric parameters (Å, º) top
Zn1—O1 | 1.863 (3) | C4—C5 | 1.357 (5) |
Zn1—O5 | 1.892 (3) | C4—H4 | 0.9300 |
Zn1—N2 | 2.017 (2) | C5—C6 | 1.404 (5) |
Zn1—N1 | 2.033 (3) | C5—H5 | 0.9300 |
P1—O1 | 1.486 (3) | C6—C7 | 1.408 (5) |
P1—O2 | 1.496 (2) | C7—C8 | 1.352 (5) |
P1—O4 | 1.546 (3) | C7—H7 | 0.9300 |
P1—O3 | 1.553 (2) | C8—C9 | 1.412 (4) |
P2—O5 | 1.496 (3) | C8—H8 | 0.9300 |
P2—O6 | 1.502 (2) | C9—C10 | 1.490 (4) |
P2—O7 | 1.542 (3) | C10—C11 | 1.392 (4) |
P2—O8 | 1.542 (3) | C11—C12 | 1.360 (5) |
O3—H3P | 0.82 (3) | C11—H11 | 0.9300 |
O4—H4P | 0.83 (3) | C12—C13 | 1.402 (5) |
O7—H7P | 0.84 (3) | C12—H12 | 0.9300 |
O8—H8P | 0.83 (3) | C13—C18 | 1.412 (4) |
N1—C9 | 1.322 (4) | C13—C14 | 1.423 (5) |
N1—C1 | 1.371 (4) | C14—C15 | 1.344 (5) |
N2—C10 | 1.339 (4) | C14—H14 | 0.9300 |
N2—C18 | 1.372 (4) | C15—C16 | 1.409 (5) |
C1—C2 | 1.405 (4) | C15—H15 | 0.9300 |
C1—C6 | 1.410 (5) | C16—C17 | 1.357 (5) |
C2—C3 | 1.357 (5) | C16—H16 | 0.9300 |
C2—H2 | 0.9300 | C17—C18 | 1.405 (5) |
C3—C4 | 1.400 (5) | C17—H17 | 0.9300 |
C3—H3 | 0.9300 | | |
| | | |
O1—Zn1—O5 | 114.53 (13) | C4—C5—C6 | 120.6 (3) |
O1—Zn1—N2 | 120.53 (11) | C4—C5—H5 | 119.7 |
O5—Zn1—N2 | 108.98 (11) | C6—C5—H5 | 119.7 |
O1—Zn1—N1 | 109.71 (13) | C5—C6—C7 | 123.5 (3) |
O5—Zn1—N1 | 117.75 (13) | C5—C6—C1 | 118.4 (3) |
N2—Zn1—N1 | 81.62 (10) | C7—C6—C1 | 118.2 (3) |
O1—P1—O2 | 113.76 (16) | C8—C7—C6 | 120.5 (3) |
O1—P1—O4 | 109.63 (18) | C8—C7—H7 | 119.8 |
O2—P1—O4 | 109.32 (14) | C6—C7—H7 | 119.8 |
O1—P1—O3 | 109.80 (15) | C7—C8—C9 | 119.0 (3) |
O2—P1—O3 | 109.34 (14) | C7—C8—H8 | 120.5 |
O4—P1—O3 | 104.59 (16) | C9—C8—H8 | 120.5 |
O5—P2—O6 | 116.24 (16) | N1—C9—C8 | 121.7 (3) |
O5—P2—O7 | 106.2 (2) | N1—C9—C10 | 116.5 (3) |
O6—P2—O7 | 110.10 (15) | C8—C9—C10 | 121.8 (3) |
O5—P2—O8 | 109.25 (17) | N2—C10—C11 | 122.2 (3) |
O6—P2—O8 | 107.69 (15) | N2—C10—C9 | 114.9 (3) |
O7—P2—O8 | 107.0 (2) | C11—C10—C9 | 122.9 (3) |
P1—O1—Zn1 | 150.5 (2) | C12—C11—C10 | 119.0 (3) |
P1—O3—H3P | 110 (3) | C12—C11—H11 | 120.5 |
P1—O4—H4P | 116 (3) | C10—C11—H11 | 120.5 |
P2—O5—Zn1 | 131.04 (18) | C11—C12—C13 | 120.5 (3) |
P2—O7—H7P | 117 (3) | C11—C12—H12 | 119.7 |
P2—O8—H8P | 116 (3) | C13—C12—H12 | 119.7 |
C9—N1—C1 | 120.6 (3) | C12—C13—C18 | 118.2 (3) |
C9—N1—Zn1 | 112.9 (2) | C12—C13—C14 | 123.3 (3) |
C1—N1—Zn1 | 126.5 (2) | C18—C13—C14 | 118.5 (3) |
C10—N2—C18 | 119.7 (3) | C15—C14—C13 | 119.9 (3) |
C10—N2—Zn1 | 113.5 (2) | C15—C14—H14 | 120.0 |
C18—N2—Zn1 | 126.6 (2) | C13—C14—H14 | 120.0 |
N1—C1—C2 | 119.7 (3) | C14—C15—C16 | 121.4 (3) |
N1—C1—C6 | 120.1 (3) | C14—C15—H15 | 119.3 |
C2—C1—C6 | 120.2 (3) | C16—C15—H15 | 119.3 |
C3—C2—C1 | 119.5 (3) | C17—C16—C15 | 120.3 (3) |
C3—C2—H2 | 120.2 | C17—C16—H16 | 119.9 |
C1—C2—H2 | 120.2 | C15—C16—H16 | 119.9 |
C2—C3—C4 | 120.8 (3) | C16—C17—C18 | 119.9 (3) |
C2—C3—H3 | 119.6 | C16—C17—H17 | 120.0 |
C4—C3—H3 | 119.6 | C18—C17—H17 | 120.0 |
C5—C4—C3 | 120.6 (3) | N2—C18—C17 | 119.8 (3) |
C5—C4—H4 | 119.7 | N2—C18—C13 | 120.2 (3) |
C3—C4—H4 | 119.7 | C17—C18—C13 | 120.0 (3) |
| | | |
O2—P1—O1—Zn1 | −165.1 (4) | C2—C1—C6—C7 | 179.6 (3) |
O4—P1—O1—Zn1 | 72.2 (5) | C5—C6—C7—C8 | −179.4 (3) |
O3—P1—O1—Zn1 | −42.2 (5) | C1—C6—C7—C8 | 0.4 (5) |
O5—Zn1—O1—P1 | 0.4 (5) | C6—C7—C8—C9 | 0.4 (5) |
N2—Zn1—O1—P1 | −132.8 (4) | C1—N1—C9—C8 | 1.8 (5) |
N1—Zn1—O1—P1 | 135.4 (4) | Zn1—N1—C9—C8 | −176.7 (2) |
O6—P2—O5—Zn1 | −3.7 (4) | C1—N1—C9—C10 | 179.2 (3) |
O7—P2—O5—Zn1 | 119.2 (3) | Zn1—N1—C9—C10 | 0.6 (3) |
O8—P2—O5—Zn1 | −125.7 (3) | C7—C8—C9—N1 | −1.6 (5) |
O1—Zn1—O5—P2 | 43.0 (3) | C7—C8—C9—C10 | −178.8 (3) |
N2—Zn1—O5—P2 | −178.6 (3) | C18—N2—C10—C11 | 3.2 (5) |
N1—Zn1—O5—P2 | −88.2 (3) | Zn1—N2—C10—C11 | −171.9 (3) |
O1—Zn1—N1—C9 | 122.5 (2) | C18—N2—C10—C9 | −176.5 (3) |
O5—Zn1—N1—C9 | −104.2 (2) | Zn1—N2—C10—C9 | 8.3 (3) |
N2—Zn1—N1—C9 | 2.9 (2) | N1—C9—C10—N2 | −6.1 (4) |
O1—Zn1—N1—C1 | −56.0 (3) | C8—C9—C10—N2 | 171.3 (3) |
O5—Zn1—N1—C1 | 77.4 (3) | N1—C9—C10—C11 | 174.2 (3) |
N2—Zn1—N1—C1 | −175.5 (3) | C8—C9—C10—C11 | −8.5 (5) |
O1—Zn1—N2—C10 | −114.3 (2) | N2—C10—C11—C12 | −2.4 (5) |
O5—Zn1—N2—C10 | 110.3 (2) | C9—C10—C11—C12 | 177.3 (3) |
N1—Zn1—N2—C10 | −6.3 (2) | C10—C11—C12—C13 | −0.4 (5) |
O1—Zn1—N2—C18 | 71.0 (3) | C11—C12—C13—C18 | 2.3 (5) |
O5—Zn1—N2—C18 | −64.5 (3) | C11—C12—C13—C14 | −177.9 (3) |
N1—Zn1—N2—C18 | 178.9 (3) | C12—C13—C14—C15 | −179.5 (3) |
C9—N1—C1—C2 | 179.2 (3) | C18—C13—C14—C15 | 0.3 (5) |
Zn1—N1—C1—C2 | −2.4 (4) | C13—C14—C15—C16 | 0.2 (5) |
C9—N1—C1—C6 | −0.9 (5) | C14—C15—C16—C17 | −0.2 (6) |
Zn1—N1—C1—C6 | 177.4 (2) | C15—C16—C17—C18 | −0.3 (5) |
N1—C1—C2—C3 | −179.3 (3) | C10—N2—C18—C17 | 178.3 (3) |
C6—C1—C2—C3 | 0.8 (5) | Zn1—N2—C18—C17 | −7.3 (4) |
C1—C2—C3—C4 | −0.7 (6) | C10—N2—C18—C13 | −1.3 (4) |
C2—C3—C4—C5 | 0.2 (6) | Zn1—N2—C18—C13 | 173.2 (2) |
C3—C4—C5—C6 | 0.2 (6) | C16—C17—C18—N2 | −178.7 (3) |
C4—C5—C6—C7 | 179.9 (3) | C16—C17—C18—C13 | 0.8 (5) |
C4—C5—C6—C1 | 0.0 (5) | C12—C13—C18—N2 | −1.5 (5) |
N1—C1—C6—C5 | 179.7 (3) | C14—C13—C18—N2 | 178.7 (3) |
C2—C1—C6—C5 | −0.5 (5) | C12—C13—C18—C17 | 179.0 (3) |
N1—C1—C6—C7 | −0.2 (5) | C14—C13—C18—C17 | −0.8 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3P···O6 | 0.82 (3) | 1.78 (2) | 2.586 (3) | 166 (4) |
O4—H4P···O2i | 0.83 (3) | 1.79 (2) | 2.616 (3) | 177 (5) |
O7—H7P···O6ii | 0.84 (3) | 1.75 (2) | 2.592 (4) | 173 (4) |
O8—H8P···O2iii | 0.83 (3) | 1.78 (2) | 2.580 (3) | 161 (4) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x+1, y, z. |
(II) (2,2'-biquinoline-
κ2N,
N')bis(dihydrogenphosphato-
κO)copper(II)/zinc(II) (0.90/0.10)
top
Crystal data top
[Zn0.90Cu0.10(H2PO4)2(C18H12N2)] | F(000) = 1047.6 |
Mr = 515.46 | Dx = 1.746 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6270 reflections |
a = 9.3801 (12) Å | θ = 3.1–24.9° |
b = 20.528 (3) Å | µ = 1.46 mm−1 |
c = 10.2991 (13) Å | T = 295 K |
β = 98.791 (2)° | Blocks, orange |
V = 1959.8 (5) Å3 | 0.20 × 0.12 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4435 independent reflections |
Radiation source: fine-focus sealed tube | 3060 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
phi and ω scans | θmax = 28.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −11→12 |
Tmin = 0.79, Tmax = 0.84 | k = −26→27 |
16359 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0413P)2] where P = (Fo2 + 2Fc2)/3 |
4435 reflections | (Δ/σ)max = 0.006 |
292 parameters | Δρmax = 0.75 e Å−3 |
4 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
[Zn0.90Cu0.10(H2PO4)2(C18H12N2)] | V = 1959.8 (5) Å3 |
Mr = 515.46 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.3801 (12) Å | µ = 1.46 mm−1 |
b = 20.528 (3) Å | T = 295 K |
c = 10.2991 (13) Å | 0.20 × 0.12 × 0.12 mm |
β = 98.791 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4435 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3060 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.84 | Rint = 0.059 |
16359 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 4 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.75 e Å−3 |
4435 reflections | Δρmin = −0.39 e Å−3 |
292 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.68190 (5) | 0.13937 (2) | 0.65242 (4) | 0.03173 (15) | 0.90 |
Cu1 | 0.68190 (5) | 0.13937 (2) | 0.65242 (4) | 0.03173 (15) | 0.10 |
P1 | 0.62641 (12) | 0.02148 (5) | 0.84848 (11) | 0.0335 (3) | |
P2 | 0.78519 (11) | 0.03656 (5) | 0.47032 (10) | 0.0320 (3) | |
O1 | 0.6235 (3) | 0.08581 (13) | 0.7814 (3) | 0.0506 (8) | |
O2 | 0.4842 (3) | −0.01266 (14) | 0.8310 (3) | 0.0476 (8) | |
O3 | 0.7432 (4) | −0.02209 (15) | 0.8014 (3) | 0.0574 (9) | |
H3P | 0.764 (5) | −0.017 (2) | 0.727 (3) | 0.069* | |
O4 | 0.6827 (3) | 0.03057 (17) | 0.9967 (3) | 0.0543 (9) | |
H4P | 0.625 (4) | 0.027 (2) | 1.051 (4) | 0.065* | |
O5 | 0.7056 (4) | 0.09718 (14) | 0.4936 (3) | 0.0575 (9) | |
O6 | 0.8554 (3) | 0.00194 (13) | 0.5915 (2) | 0.0393 (7) | |
O7 | 0.6823 (4) | −0.01171 (16) | 0.3919 (3) | 0.0602 (9) | |
H7P | 0.637 (5) | 0.004 (2) | 0.323 (3) | 0.072* | |
O8 | 0.8967 (3) | 0.05749 (18) | 0.3825 (3) | 0.0663 (11) | |
H8P | 0.980 (3) | 0.041 (2) | 0.393 (5) | 0.080* | |
N1 | 0.5628 (3) | 0.22109 (14) | 0.6213 (3) | 0.0289 (7) | |
N2 | 0.8395 (3) | 0.20542 (15) | 0.7119 (3) | 0.0308 (7) | |
C1 | 0.4181 (4) | 0.22440 (18) | 0.5749 (4) | 0.0313 (9) | |
C2 | 0.3402 (4) | 0.1664 (2) | 0.5457 (4) | 0.0383 (10) | |
H2A | 0.3863 | 0.1263 | 0.5593 | 0.046* | |
C3 | 0.1970 (5) | 0.1692 (2) | 0.4973 (4) | 0.0460 (11) | |
H3A | 0.1449 | 0.1309 | 0.4782 | 0.055* | |
C4 | 0.1284 (5) | 0.2293 (2) | 0.4763 (4) | 0.0489 (12) | |
H4A | 0.0306 | 0.2304 | 0.4426 | 0.059* | |
C5 | 0.1998 (5) | 0.2858 (2) | 0.5036 (4) | 0.0462 (11) | |
H5A | 0.1516 | 0.3253 | 0.4884 | 0.055* | |
C6 | 0.3482 (4) | 0.28484 (19) | 0.5555 (4) | 0.0345 (10) | |
C7 | 0.4307 (5) | 0.3412 (2) | 0.5874 (4) | 0.0424 (11) | |
H7A | 0.3871 | 0.3819 | 0.5766 | 0.051* | |
C8 | 0.5735 (5) | 0.3368 (2) | 0.6339 (4) | 0.0400 (10) | |
H8A | 0.6281 | 0.3742 | 0.6553 | 0.048* | |
C9 | 0.6375 (4) | 0.27542 (18) | 0.6491 (4) | 0.0319 (9) | |
C10 | 0.7945 (4) | 0.26645 (19) | 0.6962 (4) | 0.0313 (9) | |
C11 | 0.8894 (5) | 0.3192 (2) | 0.7248 (4) | 0.0409 (11) | |
H11A | 0.8562 | 0.3617 | 0.7115 | 0.049* | |
C12 | 1.0289 (5) | 0.3075 (2) | 0.7717 (4) | 0.0465 (11) | |
H12A | 1.0926 | 0.3422 | 0.7903 | 0.056* | |
C13 | 1.0791 (5) | 0.2436 (2) | 0.7929 (4) | 0.0422 (11) | |
C14 | 1.2230 (5) | 0.2276 (3) | 0.8441 (4) | 0.0549 (13) | |
H14A | 1.2896 | 0.2608 | 0.8675 | 0.066* | |
C15 | 1.2653 (5) | 0.1651 (3) | 0.8596 (4) | 0.0591 (14) | |
H15A | 1.3610 | 0.1556 | 0.8922 | 0.071* | |
C16 | 1.1670 (5) | 0.1139 (3) | 0.8274 (4) | 0.0547 (13) | |
H16A | 1.1974 | 0.0709 | 0.8399 | 0.066* | |
C17 | 1.0272 (4) | 0.1273 (2) | 0.7779 (4) | 0.0424 (11) | |
H17A | 0.9623 | 0.0934 | 0.7557 | 0.051* | |
C18 | 0.9807 (4) | 0.1922 (2) | 0.7602 (4) | 0.0341 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0341 (3) | 0.0255 (3) | 0.0355 (3) | 0.0021 (2) | 0.0051 (2) | 0.0010 (2) |
Cu1 | 0.0341 (3) | 0.0255 (3) | 0.0355 (3) | 0.0021 (2) | 0.0051 (2) | 0.0010 (2) |
P1 | 0.0346 (6) | 0.0310 (6) | 0.0363 (6) | −0.0026 (5) | 0.0098 (5) | 0.0040 (5) |
P2 | 0.0333 (6) | 0.0328 (6) | 0.0302 (6) | 0.0049 (5) | 0.0057 (5) | −0.0012 (5) |
O1 | 0.066 (2) | 0.0309 (16) | 0.062 (2) | 0.0068 (15) | 0.0312 (17) | 0.0129 (14) |
O2 | 0.0470 (18) | 0.063 (2) | 0.0324 (17) | −0.0226 (16) | 0.0048 (14) | 0.0010 (15) |
O3 | 0.073 (2) | 0.0459 (19) | 0.063 (2) | 0.0219 (17) | 0.0392 (19) | 0.0239 (17) |
O4 | 0.0433 (19) | 0.080 (2) | 0.040 (2) | −0.0237 (18) | 0.0073 (15) | −0.0024 (17) |
O5 | 0.089 (3) | 0.0470 (19) | 0.0358 (18) | 0.0304 (17) | 0.0063 (17) | −0.0030 (15) |
O6 | 0.0372 (16) | 0.0481 (18) | 0.0339 (16) | 0.0099 (14) | 0.0098 (13) | 0.0063 (13) |
O7 | 0.069 (2) | 0.048 (2) | 0.055 (2) | −0.0094 (18) | −0.0162 (18) | 0.0059 (17) |
O8 | 0.043 (2) | 0.093 (3) | 0.066 (2) | 0.0218 (19) | 0.0211 (18) | 0.043 (2) |
N1 | 0.0303 (18) | 0.0261 (17) | 0.0310 (18) | 0.0018 (14) | 0.0070 (15) | 0.0001 (14) |
N2 | 0.0315 (19) | 0.0311 (19) | 0.0295 (18) | −0.0024 (15) | 0.0038 (15) | −0.0022 (14) |
C1 | 0.036 (2) | 0.033 (2) | 0.027 (2) | 0.0018 (19) | 0.0109 (18) | 0.0027 (17) |
C2 | 0.037 (2) | 0.035 (2) | 0.044 (3) | −0.002 (2) | 0.010 (2) | 0.002 (2) |
C3 | 0.037 (3) | 0.055 (3) | 0.046 (3) | −0.007 (2) | 0.007 (2) | 0.000 (2) |
C4 | 0.027 (2) | 0.072 (4) | 0.046 (3) | 0.004 (2) | 0.002 (2) | 0.009 (3) |
C5 | 0.042 (3) | 0.053 (3) | 0.046 (3) | 0.017 (2) | 0.013 (2) | 0.011 (2) |
C6 | 0.039 (2) | 0.036 (2) | 0.030 (2) | 0.009 (2) | 0.0118 (19) | 0.0080 (18) |
C7 | 0.053 (3) | 0.029 (2) | 0.046 (3) | 0.013 (2) | 0.012 (2) | 0.007 (2) |
C8 | 0.048 (3) | 0.025 (2) | 0.047 (3) | 0.001 (2) | 0.008 (2) | 0.0004 (19) |
C9 | 0.040 (2) | 0.026 (2) | 0.030 (2) | −0.0021 (18) | 0.0078 (19) | 0.0010 (17) |
C10 | 0.038 (2) | 0.031 (2) | 0.026 (2) | −0.0023 (19) | 0.0080 (18) | −0.0029 (17) |
C11 | 0.044 (3) | 0.033 (2) | 0.046 (3) | −0.008 (2) | 0.009 (2) | −0.008 (2) |
C12 | 0.048 (3) | 0.048 (3) | 0.043 (3) | −0.020 (2) | 0.007 (2) | −0.015 (2) |
C13 | 0.035 (2) | 0.064 (3) | 0.029 (2) | −0.009 (2) | 0.0095 (19) | −0.007 (2) |
C14 | 0.034 (3) | 0.087 (4) | 0.043 (3) | −0.007 (3) | 0.005 (2) | −0.013 (3) |
C15 | 0.028 (2) | 0.102 (4) | 0.046 (3) | 0.009 (3) | 0.002 (2) | −0.008 (3) |
C16 | 0.051 (3) | 0.065 (3) | 0.049 (3) | 0.020 (3) | 0.008 (2) | 0.000 (3) |
C17 | 0.036 (2) | 0.046 (3) | 0.044 (3) | 0.007 (2) | 0.002 (2) | −0.002 (2) |
C18 | 0.033 (2) | 0.044 (3) | 0.027 (2) | −0.004 (2) | 0.0090 (18) | −0.0048 (18) |
Geometric parameters (Å, º) top
Zn1—O1 | 1.870 (3) | C4—C5 | 1.348 (6) |
Zn1—O5 | 1.894 (3) | C4—H4A | 0.9300 |
Zn1—N1 | 2.014 (3) | C5—C6 | 1.412 (6) |
Zn1—N2 | 2.030 (3) | C5—H5A | 0.9300 |
P1—O1 | 1.488 (3) | C6—C7 | 1.403 (6) |
P1—O2 | 1.493 (3) | C7—C8 | 1.355 (6) |
P1—O3 | 1.548 (3) | C7—H7A | 0.9300 |
P1—O4 | 1.548 (3) | C8—C9 | 1.394 (5) |
P2—O5 | 1.489 (3) | C8—H8A | 0.9300 |
P2—O6 | 1.498 (3) | C9—C10 | 1.490 (5) |
P2—O7 | 1.525 (3) | C10—C11 | 1.404 (5) |
P2—O8 | 1.544 (3) | C11—C12 | 1.346 (6) |
O3—H3P | 0.82 (3) | C11—H11A | 0.9300 |
O4—H4P | 0.84 (4) | C12—C13 | 1.400 (6) |
O7—H7P | 0.83 (3) | C12—H12A | 0.9300 |
O8—H8P | 0.85 (3) | C13—C18 | 1.408 (5) |
N1—C9 | 1.325 (5) | C13—C14 | 1.411 (6) |
N1—C1 | 1.371 (5) | C14—C15 | 1.346 (7) |
N2—C10 | 1.324 (5) | C14—H14A | 0.9300 |
N2—C18 | 1.369 (5) | C15—C16 | 1.404 (7) |
C1—C6 | 1.403 (5) | C15—H15A | 0.9300 |
C1—C2 | 1.405 (5) | C16—C17 | 1.360 (6) |
C2—C3 | 1.361 (5) | C16—H16A | 0.9300 |
C2—H2A | 0.9300 | C17—C18 | 1.405 (5) |
C3—C4 | 1.392 (6) | C17—H17A | 0.9300 |
C3—H3A | 0.9300 | | |
| | | |
O1—Zn1—O5 | 115.51 (13) | C4—C5—C6 | 119.8 (4) |
O1—Zn1—N1 | 112.78 (12) | C4—C5—H5A | 120.1 |
O5—Zn1—N1 | 112.29 (12) | C6—C5—H5A | 120.1 |
O1—Zn1—N2 | 117.21 (13) | C1—C6—C7 | 117.8 (4) |
O5—Zn1—N2 | 112.95 (13) | C1—C6—C5 | 118.6 (4) |
N1—Zn1—N2 | 81.50 (13) | C7—C6—C5 | 123.6 (4) |
O1—P1—O2 | 114.05 (18) | C8—C7—C6 | 120.5 (4) |
O1—P1—O3 | 109.34 (16) | C8—C7—H7A | 119.7 |
O2—P1—O3 | 110.64 (19) | C6—C7—H7A | 119.7 |
O1—P1—O4 | 109.26 (19) | C7—C8—C9 | 119.1 (4) |
O2—P1—O4 | 109.84 (16) | C7—C8—H8A | 120.5 |
O3—P1—O4 | 103.1 (2) | C9—C8—H8A | 120.5 |
O5—P2—O6 | 115.42 (16) | N1—C9—C8 | 122.2 (4) |
O5—P2—O7 | 109.6 (2) | N1—C9—C10 | 115.5 (3) |
O6—P2—O7 | 107.14 (17) | C8—C9—C10 | 122.4 (4) |
O5—P2—O8 | 105.24 (19) | N2—C10—C11 | 121.6 (4) |
O6—P2—O8 | 111.65 (17) | N2—C10—C9 | 116.0 (3) |
O7—P2—O8 | 107.5 (2) | C11—C10—C9 | 122.4 (4) |
P1—O1—Zn1 | 149.82 (18) | C12—C11—C10 | 119.2 (4) |
P1—O3—H3P | 120 (3) | C12—C11—H11A | 120.4 |
P1—O4—H4P | 119 (3) | C10—C11—H11A | 120.4 |
P2—O5—Zn1 | 130.50 (18) | C11—C12—C13 | 120.6 (4) |
P2—O7—H7P | 114 (4) | C11—C12—H12A | 119.7 |
P2—O8—H8P | 121 (4) | C13—C12—H12A | 119.7 |
C9—N1—C1 | 119.8 (3) | C12—C13—C18 | 118.2 (4) |
C9—N1—Zn1 | 113.9 (3) | C12—C13—C14 | 123.7 (4) |
C1—N1—Zn1 | 126.3 (3) | C18—C13—C14 | 118.1 (4) |
C10—N2—C18 | 120.3 (3) | C15—C14—C13 | 120.9 (5) |
C10—N2—Zn1 | 113.0 (3) | C15—C14—H14A | 119.6 |
C18—N2—Zn1 | 126.6 (3) | C13—C14—H14A | 119.6 |
N1—C1—C6 | 120.7 (4) | C14—C15—C16 | 121.0 (5) |
N1—C1—C2 | 119.2 (4) | C14—C15—H15A | 119.5 |
C6—C1—C2 | 120.2 (4) | C16—C15—H15A | 119.5 |
C3—C2—C1 | 119.6 (4) | C17—C16—C15 | 119.9 (5) |
C3—C2—H2A | 120.2 | C17—C16—H16A | 120.1 |
C1—C2—H2A | 120.2 | C15—C16—H16A | 120.1 |
C2—C3—C4 | 120.1 (4) | C16—C17—C18 | 120.2 (4) |
C2—C3—H3A | 119.9 | C16—C17—H17A | 119.9 |
C4—C3—H3A | 119.9 | C18—C17—H17A | 119.9 |
C5—C4—C3 | 121.8 (4) | N2—C18—C13 | 120.0 (4) |
C5—C4—H4A | 119.1 | N2—C18—C17 | 120.0 (4) |
C3—C4—H4A | 119.1 | C13—C18—C17 | 120.0 (4) |
| | | |
O2—P1—O1—Zn1 | −114.6 (4) | C4—C5—C6—C7 | −179.6 (4) |
O3—P1—O1—Zn1 | 9.8 (5) | C1—C6—C7—C8 | 0.8 (6) |
O4—P1—O1—Zn1 | 122.0 (4) | C5—C6—C7—C8 | −178.4 (4) |
O5—Zn1—O1—P1 | 34.5 (5) | C6—C7—C8—C9 | 0.2 (6) |
N1—Zn1—O1—P1 | 165.5 (4) | C1—N1—C9—C8 | 0.5 (5) |
N2—Zn1—O1—P1 | −102.4 (4) | Zn1—N1—C9—C8 | −180.0 (3) |
O6—P2—O5—Zn1 | 1.7 (3) | C1—N1—C9—C10 | −178.8 (3) |
O7—P2—O5—Zn1 | 122.8 (3) | Zn1—N1—C9—C10 | 0.7 (4) |
O8—P2—O5—Zn1 | −121.9 (3) | C7—C8—C9—N1 | −0.9 (6) |
O1—Zn1—O5—P2 | −49.3 (3) | C7—C8—C9—C10 | 178.3 (4) |
N1—Zn1—O5—P2 | 179.5 (2) | C18—N2—C10—C11 | 1.7 (5) |
N2—Zn1—O5—P2 | 89.5 (3) | Zn1—N2—C10—C11 | −176.4 (3) |
O1—Zn1—N1—C9 | 117.3 (3) | C18—N2—C10—C9 | −177.2 (3) |
O5—Zn1—N1—C9 | −110.1 (3) | Zn1—N2—C10—C9 | 4.7 (4) |
N2—Zn1—N1—C9 | 1.3 (3) | N1—C9—C10—N2 | −3.7 (5) |
O1—Zn1—N1—C1 | −63.2 (3) | C8—C9—C10—N2 | 177.0 (3) |
O5—Zn1—N1—C1 | 69.4 (3) | N1—C9—C10—C11 | 177.4 (3) |
N2—Zn1—N1—C1 | −179.2 (3) | C8—C9—C10—C11 | −1.9 (6) |
O1—Zn1—N2—C10 | −114.7 (3) | N2—C10—C11—C12 | −1.3 (6) |
O5—Zn1—N2—C10 | 107.3 (3) | C9—C10—C11—C12 | 177.5 (4) |
N1—Zn1—N2—C10 | −3.4 (2) | C10—C11—C12—C13 | −0.5 (6) |
O1—Zn1—N2—C18 | 67.3 (3) | C11—C12—C13—C18 | 1.8 (6) |
O5—Zn1—N2—C18 | −70.7 (3) | C11—C12—C13—C14 | −178.7 (4) |
N1—Zn1—N2—C18 | 178.6 (3) | C12—C13—C14—C15 | −178.6 (4) |
C9—N1—C1—C6 | 0.5 (5) | C18—C13—C14—C15 | 0.8 (6) |
Zn1—N1—C1—C6 | −178.9 (3) | C13—C14—C15—C16 | −1.1 (7) |
C9—N1—C1—C2 | 180.0 (3) | C14—C15—C16—C17 | 1.0 (7) |
Zn1—N1—C1—C2 | 0.5 (5) | C15—C16—C17—C18 | −0.7 (6) |
N1—C1—C2—C3 | −178.8 (3) | C10—N2—C18—C13 | −0.3 (5) |
C6—C1—C2—C3 | 0.6 (6) | Zn1—N2—C18—C13 | 177.6 (3) |
C1—C2—C3—C4 | 0.3 (6) | C10—N2—C18—C17 | 179.3 (3) |
C2—C3—C4—C5 | −0.5 (7) | Zn1—N2—C18—C17 | −2.8 (5) |
C3—C4—C5—C6 | −0.3 (7) | C12—C13—C18—N2 | −1.4 (6) |
N1—C1—C6—C7 | −1.1 (5) | C14—C13—C18—N2 | 179.1 (3) |
C2—C1—C6—C7 | 179.4 (4) | C12—C13—C18—C17 | 179.0 (4) |
N1—C1—C6—C5 | 178.1 (3) | C14—C13—C18—C17 | −0.5 (6) |
C2—C1—C6—C5 | −1.4 (6) | C16—C17—C18—N2 | −179.2 (4) |
C4—C5—C6—C1 | 1.2 (6) | C16—C17—C18—C13 | 0.5 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3P···O6 | 0.82 (3) | 1.79 (2) | 2.593 (4) | 163 (5) |
O4—H4P···O2i | 0.84 (4) | 1.73 (2) | 2.567 (4) | 174 (5) |
O7—H7P···O2ii | 0.83 (3) | 1.81 (2) | 2.620 (4) | 163 (5) |
O8—H8P···O6iii | 0.85 (3) | 1.76 (2) | 2.603 (4) | 173 (5) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1; (iii) −x+2, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Zn0.88Cu0.12(H2PO4)2(C18H12N2)] | [Zn0.90Cu0.10(H2PO4)2(C18H12N2)] |
Mr | 515.42 | 515.46 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 298 | 295 |
a, b, c (Å) | 7.8089 (12), 10.5225 (17), 12.3618 (19) | 9.3801 (12), 20.528 (3), 10.2991 (13) |
α, β, γ (°) | 91.787 (2), 91.722 (2), 106.632 (3) | 90, 98.791 (2), 90 |
V (Å3) | 972.0 (3) | 1959.8 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.46 | 1.46 |
Crystal size (mm) | 0.26 × 0.12 × 0.08 | 0.20 × 0.12 × 0.12 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.79, 0.89 | 0.79, 0.84 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7214, 4216, 3529 | 16359, 4435, 3060 |
Rint | 0.025 | 0.059 |
(sin θ/λ)max (Å−1) | 0.663 | 0.662 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.136, 1.14 | 0.059, 0.109, 1.02 |
No. of reflections | 4216 | 4435 |
No. of parameters | 292 | 292 |
No. of restraints | 4 | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −0.38 | 0.75, −0.39 |
Selected bond lengths (Å) for (I) topZn1—O1 | 1.863 (3) | P1—O4 | 1.546 (3) |
Zn1—O5 | 1.892 (3) | P1—O3 | 1.553 (2) |
Zn1—N2 | 2.017 (2) | P2—O5 | 1.496 (3) |
Zn1—N1 | 2.033 (3) | P2—O6 | 1.502 (2) |
P1—O1 | 1.486 (3) | P2—O7 | 1.542 (3) |
P1—O2 | 1.496 (2) | P2—O8 | 1.542 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3P···O6 | 0.82 (3) | 1.78 (2) | 2.586 (3) | 166 (4) |
O4—H4P···O2i | 0.83 (3) | 1.79 (2) | 2.616 (3) | 177 (5) |
O7—H7P···O6ii | 0.84 (3) | 1.75 (2) | 2.592 (4) | 173 (4) |
O8—H8P···O2iii | 0.83 (3) | 1.78 (2) | 2.580 (3) | 161 (4) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x+1, y, z. |
Table 3. π–π contacts (Å, °) in (I) topCg···Cg | ccd | sa | ipd |
Cg1···Cg1iv | 3.595 (2) | 21.78 (1) | 3.338 (1) |
Cg1···Cg3iv | 3.613 (2) | 22.92 (8) | 3.330 (4) |
Cg1···Cg4v | 4.248 (2) | 38.(3.) | 3.33 (13) |
Cg2···Cg2v | 3.911 (2) | 27.38 (1) | 3.473 (1) |
Cg2···Cg4v | 3.779 (3) | 23.5 (8) | 3.46 (2) |
Cg2···Cg4vi | 4.094 (3) | 35.0 (7) | 3.35 (3) |
Symmetry codes: (iv) -x+1,-y+2,-z; (v) -x+1,-y+2,-z+1; (vi) -x+2,-y+2,-z+1.
For centroid definition, see Fig. 1. ccd: centroid-to-centroid distance; sa: (mean) slippage angle;
ipd: (mean) interplanar distance |
Selected bond lengths (Å) for (II) topZn1—O1 | 1.870 (3) | P1—O3 | 1.548 (3) |
Zn1—O5 | 1.894 (3) | P1—O4 | 1.548 (3) |
Zn1—N1 | 2.014 (3) | P2—O5 | 1.489 (3) |
Zn1—N2 | 2.030 (3) | P2—O6 | 1.498 (3) |
P1—O1 | 1.488 (3) | P2—O7 | 1.525 (3) |
P1—O2 | 1.493 (3) | P2—O8 | 1.544 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3P···O6 | 0.82 (3) | 1.79 (2) | 2.593 (4) | 163 (5) |
O4—H4P···O2i | 0.84 (4) | 1.73 (2) | 2.567 (4) | 174 (5) |
O7—H7P···O2ii | 0.83 (3) | 1.81 (2) | 2.620 (4) | 163 (5) |
O8—H8P···O6iii | 0.85 (3) | 1.76 (2) | 2.603 (4) | 173 (5) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1; (iii) −x+2, −y, −z+1. |
Table 6. π–π contacts (Å, °) in (II) topCg···Cg | ccd | sa | ipd |
Cg1···Cg2iv | 3.747 (2) | 24.42 (1) | 3.412 (1) |
Cg1···Cg4iv | 3.522 (2) | 14.7 (2) | 3.405 (4) |
Cg2···Cg3v | 4.183 (2) | 37.2 (2) | 3.33 (1) |
Cg2···Cg3vi | 3.509 (2) | 13.9 (3) | 3.405 (4) |
Cg3···Cg4vii | 3.574 (2) | 18.9 (9) | 3.38 (3) |
Symmetry codes: (iv) x-1/2,-y+1/2,z-1/2; (v) x+1,y,z;
(vi) x+1/2,-y+1/2,z+1/2; (vii) x-1,y, z.
For centroid definition, see Fig. 1. ccd: centroid-to-centroid distance; sa: (mean) slippage angle;
ipd: (mean) interplanar distance |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
The synthesis of hybrid organic–inorganic open-framework materials has been a subject of intense research owing to their interesting structural chemistry and potential applications in such different areas as ion exchange, adsorption and catalysis, the search for new physical properties etc. (Hagrman et al., 1999; Férey, 2001; Eddaoudi et al., 2001; Davis, 2002). A particular and effective method to obtain these compounds is hydrothermal synthesis, as the generation of a product by a chemical reaction in a sealed, heated solution above ambient pressure is usually referred to. The mechanisms involved are not fully understood yet, but the ability of the process to generate novel products unattainable otherwise is well known, and the products can possess peculiar characteristics regarding, for instance, binding affinity (Feng & Xu, 2001; Moghimi et al., 2003; Walton, 2002). The present report on two polymorphic forms of a mononuclear biquinoline dihydrogenphosphate obtained from a reaction between zinc, copper, phosphate and biquinoline might serve as an example of such capability. A search in the January 2007 release of the Cambridge Structural Database (CSD; Allen, 2002) revealed that the few reported zinc or copper phosphates that include chelating dinitrogenated bases in their structures are poly-, oligo- or at least dimeric entities; no mononuclear zinc or copper phosphate including bipyridine, phenathroline, biquinoline etc. seems to have been structurally characterized, and the present compound [zinc/copper biquinoline dihydrogenphosphate, ZnxCu1 - x(biq)(H2PO4)2; biq is biquinoline] appears to be the first reported occurrence of such a structure. The title compound was obtained serendipitously as a by-product of a hydrothermal synthesis (see details in the Experimental section) in the form of two different polymorphic varieties, viz. a triclinic form (I), space group P1, x = 0.88 (1), and a monoclinic form (II), space group P21/n, x = 0.90 (2).
Fig. 1 shows that the two forms are structurally very similar, with the mixed cation chelated by a biquinoline unit through its two N atoms, and two monocoordinated dihydrogenphosphates completing the distorted tetrahedral environment. No meaningful differences regarding coordination distances and angles exist between the two polyhedra (see Tables 1 and 4 and Fig. 2 for a direct comparison), nor is there any significant evidence of structural stress due to solid solution formation, short of a minor transverse elongation of the displacement ellipsoids of the bound phosphate O atoms, which might represent a slight positional disorder.
However, and in spite of their similarities, polymorph (I) appears slightly more strained than (II), as suggested by a comparison of the dihedral angles between the N/Zn/N and the O/Zn/O coordination planes, that in (I) being significantly larger [98.7 (1) versus 91.8 (1)°]. The same applies for the angles between the lateral wings of the biquinoline ligand [8.7 (1) versus 1.2 (1)°].
The dihydrogenphosphate anions coordinate through one of their unprotonated O atoms, the remaining one being the acceptor of an intramolecular hydrogen bond linking both dihydrogenphosphate groups into a single unit. The interaction of this O atom seems to be strong enough to partially weaken its bond to the P atom. In fact, and contrary to what would be expected, the P═Ouncoord distances are slightly longer than the P—Ocoord bonds in all four independent units, and even though these differences are rather small in terms of the individual s.u. values, the fact that all four behave in the same way seems to give this behaviour some significance. On the other hand, this fact does not appear to be unusual; a search of the CSD showed some 50 cases of singly coordinated phosphates, in half of which a similar situation arises.
The P—OH distances lie in a narrow range, as do the P═O distances, and the P—OH and P═O bonds have well differentiated values in both structures, with means of 1.546 (7) and 1.495 (7) Å for (I), and 1.541 (16) and 1.492 (6) Å for (II). There is a subtle difference between the polymorphs, however, which is influential because of its effects upon the otherwise very similar packing schemes; this difference is the rotation of the phosphate groups around the P1—O1 and P2—O5 axes, in opposite directions, as a result of the restraint imposed by the very strong intramolecular hydrogen bond (O3—H3P···O6) linking the two phosphate groups. This relative rotation, as measured by the differences in the relevant torsion angles (Zn1—O1—P1—O3 and Zn1—O5—P2—O6), is 52 (1) and 5 (1)° for the P1 and P2 phosphate groups, respectively, and its main consequence is the different orientation in space of the remaining three Hphosphate atoms prone to intermolecular hydreogen bonding, which in both structures determines the formation of two-dimensional structures parallel to (010). The first interactions listed in Tables 2 and 5 consist of intramolecular hydrogen bonds (see Fig. 1); the following two define chains that run along [-101], in turn connected (roughly along [101]) via the fourth interaction. Figs. 3 and 4 show a simplified view of these two-dimensional structures The diverse phosphate orientations can be seen reflected in the size of the `holes' built up around the symmetry centres at (0, 1/2, 1), (1/2, 1/2, 1/2) and (1, 1/2, 0), labelled as A and B, respectively, in Figs. 3 and 4; those in (I) are large and even, while those in (II) alternate in size along the [101] direction.
In the two-dimensional structures, the biquinoline groups (schematized in Figs. 3 and 4) protrude outwards at both sides, in such a way as to interdigitate when the planes sack along b. The interaction between adjacent planes is achieved through π–π contacts involving aromatic rings in neighbouring biquinoline groups, the main interactions being summarized in Tables 3 and 6.